Carbalkoxy aminoanthraquinone sulfonamides



Patented Nov. 2, i948 I l cAaeA ox A NQANTHRA UINQNE;

sU FoNAMI Es Edganl-EaRenfrew; Jr.,Phillipsburg, N. J assignor toy Generai-Aniline gz Film Corporation, New

York,N. -Y,, a corporation of Delaware No Drawing. Applicationuunem, 194e,.

SerialNo.6'78,357

v s oia msQ (01. 260-372) Thisinvention relates-tonew compoundsymore anthraquinone sulfonarnides of the general particularly to improvedwacid dyestuffs of the formula; l aminoanthraquinone series which in the free state i may bezrepresented byEthe general formula ere n Z as fiqance ioresaidhe by wherein R represents an alkyl radical and Z a est erificationgcan, citiii'ie .P JP JK I WH 1 13 sulfonamide radical which maybe of the formula: her with the aid of acid catalyst f such as; hydrochloric or sulfuric acid For the forma -S0zNH-X X e t r" rou in r r m 1am t d y alip c mo ohi dri alqehqls re-em eye lora ampl r ethr alcqhql hrlalceh is pro rl- Y i alcohol, n-butyl al cohol'gis obutyl alcohol sec -n or" butyl lcohol; te if -l u r 'eehelhnrhe rll elcpi oll j2-ethyl-n-hexy1 alcohol; n-octyl alcohol; etc. so \f The carboxylic aminoanthraquinone sulfony l y l amides serving as starting materials for the pro wh r in-X rand =Y','-eacl'-i "represent a "saturated; duction of thelnew dyestuffsmay be, prepared by, aliphatioradical," suchuas alkyl radicals or alkyl ring n t t r i an queous, mediumw 1- radicals, containing carboxy', carbalkoxy alkoxy, 3O amino-4brommanthraquinoner,2sulfonic acid acy-loxyx hydrcxy, halogen, sulfo and secondary s m Salt, fa n lf nam de, Whig and: tertiary .alk'ylamino groups, or 4 an aromatic: dros n 0 QQEPQOLSUQh ,Q S SO i111n.,ca 'b0nate0 radicalnofrthebenzene, naphthalene and hydrobicarbonate, and ,a catalyst, such as, copper, genated naphthaleneseriesgandgA represents a cuprous or cupi icsalts, e. g., cuprousvchlorida bivalentralkylene radical which with the nitrogen 35 and heating, until condensat 1, sr mpleli he atom on thel sulfonyl groupconstitutes a 5 to 7 productsulfon mide'maybe-is lated andtherem membered heterocyclic ringer after purifi edby means of welt-known procedures.

The new carbalkoxy aminoanthraquinone 5111- he m no en nes e d empl yed in; fonamides dye animaland nylon risuper-polythe product o of e c bea li amia -anthra:gamide) fibers from acid orgneutral bath; edd sh- 40 1 1 1 1 ly onem e ma be:preparedwbyfreac blue to blue to greenish-blue clear shades of good m hlprobenzo Q W f hlo s lfen q a dt fastness properties. They are characterized by Obtain the carboxy h or e ze u n q dyeing deeper shades from-neutral bath than the which in turn, is 6 C' d '1W I l t dpr corresponding carboxylic aminoanthraquinone mary or secondary amino compoun or l cyc id sulfonarnides, a valuable property advantageous 4551111116 pl w carbpxychlorobenzenesul-- in the union dyeing of fabrics; containing fibers fonamide. The latter isthen aminated with amwhich become: tendered on; treatment with acid, monium hydroxide-in the presence of a copper such as cotton and rayon. catalyst, e. g., copper sul fate to obtain the de- The new ester compounda maybe prepared by sired am-inobenzenesulfonamide.

esterifying the corresponding carboxylic amino- 50' Among the amino'compounds which may be employed for the preparation of the afore-defined aminobenzenesulfonamides are, for example, monoand di-methyl amine, monoand di-ethyl amine, monoand di-isopropyl amine, cyclohexylamine, hexahydrobenzylamine, hexahydroanthranilic acid, N-methyl glycine, glycine, alanine, ethyl w aminocaproate, taurine, N methyl taurine, fi-aminoethyl acetate, monoand diethanolamine, [3-ethoxyethylamine, ,B-bromoethylamine, p-toluidine, -amino-o-xylene, 2- nitro-p-anisidine, o, mor p-aminobenzoic acid, -aminosalicylic acid, 2-amino-4-methylbenzoic acid, 5-nitro-2-aminobenzoic acid, 2- chloro-p-aminobenzoic acid, aniline-o-, mor p-sulfonic acid, p-phenylenediamine, l-hydroxy- 4-amino-2-naphthoic acid, 3-hydroxy-7-amino- 2-naphthoic acid, ac.-tetrahydro-a-naphthylamine, and ar.-tetrahydro-a-naphthylamine, etc. Among the alicyclic imines suitable for the preparation of the aminobenzenesulfonamides may be mentioned, for example, tetramethylene imine (pyrrolidine) pentainethylene imine (piperidine) 2- and 3-methylpiperidine, hexamethylene imine, etc.

The new ester dyestufis may also be prepared following theprocess for the preparation of the oarboxylic aminoanthraquinone sulfanamides with the exception that instead of employing the 'carboxy-aminobenzenesulfonamides, the correspondng carbalkoxy compounds are employed. Proceeding in this manner for their preparation, more than one ester group may be introduced into the molecule of the dyestuffs by starting with carbalkoxy-aminobenzenesulfonamides from the condensation of a carbalkoxy-aminobenzenesulfonylchloride with, for example, an aminobenzoic acid-alkylester, the ester-alkyl radical of which may be the same or different than that of the carbalkoxy aminobenzenesulfonylchloride. For

example, 5-sulfonchloride-anthranilic acid-ethylfonamides is further illustrated bythe following specific examples, to which, however, it is not intended that it be limited. Parts are by weight.

Example 1 A solution of 25 parts of 5-(2'-carboxyphenylsulfamyD-anthrani-lic acid in 300 parts of water containing 30.2 parts of sodium bicarbonate was added to 20.2 parts of l-aminol-bromoanthraquinone-Z-sulfonic acid sodium salt in 200 parts of water. 1.5 parts of cuprous chloride was then added and the mixture heated under stirring at 75 C. for 18 hours. At the end of this time the mixture was a deep ruby color to which, after cooling, was added 60 parts of concentrated hydrochloric acid. The dyestufi settled out in the form of large non-sticky masses which were isolated by decantation.

To purify the dyestufi, it was dispersed in 500 parts of water at 60 0., the resulting solution filtered, and to the deeply blue filtrate at 60 C. was added suflicient sodium chloride to precipitate the dyestuff. After separation by filtration, the

dyestuif was again subjected to the dissolution and precipitation steps, whereupon the precipitate was washed with sodium chloride solution aqueous). The purified dyestufi" was dried at 90 C. and ground. It has the formula:

0 NHz H -sou1 II 0 NH 0 3 SO2NH ExampleZ The reflux condenser was exchanged for a downward distillation condenser and the unreacted alcohol removed by distillation. To the red residue was added 100 parts of water and sufii-' cient ammonia to give a faintly basic mixture. A few drops of hydrochloric acid was added and the nearly neutral suspension dried. The dyestuff product has the formula: y

(I) NHz S OM it gave deeper shades than did the unesterified starting dyestufi'.

Ewample 3 A mixture of parts of n-butyl alcohol, 5 parts of the starting carboxylic aminoanthraquinone sulfonamide of Example 1 and 9 parts of concentrated sulfuric acid was heated at the boiling point under reflux for 12 hours. The reaction mixture was cooled, filtered and the cake stirred with 50 parts of water and sufiicient ammonia to give a faintly alkaline mixture. The slurry was evaporated to dryness and the desiccate ground The product dyestuff has the formula:

0 NHz -SO3H -0 O OCAHB C OOCrHa some and dyes wool in bright blue shades. The new dyestuff gives distinctly deeper shades than the unesterified starting dyestuff when dyeing by the neutral bath. l i

Example 4 Into 80 parts of absolute ethanol was placed 5 parts of the carboxylic dyestufi of the formula, 1- aminoanthraquinone 4 N-[5--diethy1sulfamylanthranilic acidl-2-sulfonic acid. 9 parts of con- 1 centrated sulfuric acid was added, and the mixture stirred at the boilingpoint for 12 hours under reflux. The reaction mixture was cooled, filtered and the cake stirred with 50 parts of water and enough ammonia torgive a faintly alkaline mixture. The slurry was evaporated to dryness. The product has the formula:

-SOH

I]. 1 O INH C O O CzHt SO2N CzHs

and dyes Wool attractive blues shades from the neutral or the acid bath. The new ester dyestuff gives deeper shades from the neutral bath than does the corresponding carboxylic dyestuff employed as starting material.

Example 5 A mixture of 80 parts of absolute ethanol, 5

parts of the carboxylic compound of the formula, l-aminoanthraquinone 4 N [5'-(cyclohexylsulfamyl) anthranilic acidl-Z-sulfonic acid, and 9 parts of concentrated sulfuric acid was heated under reflux at the boiling temperature for 12 hours, The product was isolated as in Example 4. It has the formula:

0 NHz ll n O IIIH COOC2H5 I H H SOzNHQH and dyes wool well from the neutral bath in reddish-blue shade.

Example 6 A mixture of 80 parts of isopropyl alcohol, 5 parts of the carboxylic compound of the formula, 1 aminoanthraquinone 4 N [5-(p-tolylsulfamyl) -anthrani1ic acidl-2-sulfonic acid, and 9 parts of concentrated sulfuric acid was heated under reflux at the boiling point for 12 hours. The product was isolated in a manner similar to 6 that described in Example 4. The product the formula:

:NHE

IITH

| somm-G-on,

and dyes wool attractive deep blue shades from both the neutral and the acid bath.

Example 7 It has the formula:

0 N H: H

SOaH

IIIH

-COOCHa (i)CH:

and dyes wool rich greenish-blue shades from either the neutral or the acid bath.

As various other embodiments of the invention will occur to those skilled in the art, it is not intended that the scope of the patent be limited except as is required by the prior art and the appended claims.

I claim:

1. An aminoanthraquinone compound of the general formula:

O NHz H SOaH H 0 NH COOK a:

COOR

wherein R, represents the same loweralkyl radical and :1: represents a radical selected-from the group consisting of hydrogen and lower alkyl.

2. The amino anthraquinone compound of the formula:

so'm COOC2H6 COOCZH! s omn EDGAR E. RENFREW, JR.

REFERENCES CITED The following references are of record in the 20 file of this patent:

UNITED STATES PATENTS Name Date Weinand et a1 Mar. 26, 1940 Number 

